Metal-acrylate curing agents

ABSTRACT

The disclosure relates to using metal acrylate compounds such as zinc diacrylate (ZDA), zinc dimethacrylate (ZDMA), among others for curing epoxy functional (and other cross-linking compounds), and to compositions containing such compounds for use in powder coat, film, adhesive, among other applications. ZDA and ZDMA containing compounds can cure the epoxy component of the compositions while being substantially free of conventional curing agents.

This application is a continuation in part of application Ser. No.10/729,339, filed on Dec. 04, 2003 now U.S. Pat. No. 7,208,538, whichclaims the benefit of U.S. Provisional Application No. 60/430,882, filedon Dec. 04, 2002. The disclosures of these patent applications arehereby incorporated by reference.

FIELD OF THE INVENTION

The subject matter of the instant invention relates to metal acrylatecuring agents. The subject matter also relates to using these curingagents to prepare useful compositions for use coatings, films adhesives,among other uses.

BACKGROUND OF THE INVENTION

Epoxy functional compounds and systems are known in this art andemployed in a wide range of applications and formulations. By “epoxyfunctional system” it is meant to refer to a mixture or blend containingat least one epoxy functional compound and at least one curing agent forthe compound. Examples of such systems comprise automotive andindustrial adhesives/sealants, corrosion resistance coatings, films andpaints, pre-preg, tapes, and hand lay-up structural composites, powdercoatings/films/paints, adhesives, films, among other applications.

It is known in this art to employ curing agents to affect or controlcross linking of epoxy functional compounds. Conventional epoxy curingagents include amines, polyamides, dicyandiamide, polysulfides,anhydrides, melamines, ureas, imidizole compounds, amidoamines,phenol/formaldehydes, boron trifluoride complexes, among otherconventional curing agents. Formulations containing such epoxy curingagents can be heat activated. While these curing agents are effective atcuring epoxy functional compounds, formulations containing these curingagents can have decreased shelf stability when catalysts are included(e.g., catalysts to decrease activation temperature), are incompatiblewith many types of fillers, produce either relatively soft or roughsurfaces, can cause paint staining, dark or discolored film, shrinkageof the compound, among other undesirable characteristics. Epoxyfunctional systems such as coatings, films, adhesives, among others,that employ conventional curing agents also suffer these negativecharacteristics. Conventional curing agents may also be environmentallyundesirable.

There is a need in this art for a curing agent for an epoxy functionalsystem that results in a cured system having improved shrinkage, clearor no color, lower curing temperature, shelf stability, less charring,increased hardness, reduced paint staining, among other properties notachieved by conventional curing agents.

SUMMARY OF THE INVENTION

The instant invention solves problems associated with conventionalcuring agents by employing an effective amount of at least one metallicacrylate, metal diacrylate, monomethylacrylate, dimethacrylatecompounds, among others. By an effective amount it is meant that theamount of metal diacrylate is sufficient to cure at least a portion ofthe resin composition, e.g., about 1 to about 50 wt. % and typicallyabout 5 to about 20 wt. % of metal diacrylate (e.g., about 6 to about 12wt %). The metal diacrylate can provide other benefits while also actingas a curing agent such as reduced shrinkage, improved clarity ortransparent coatings, improved heat aging, improved shelf life. Whileany suitable metal diacrylate can be employed, examples of suitablediacrylates comprise at least one member selected from the groupconsisting of zinc diacrylate (ZDA), zinc dimethacrylate (ZDMA),magnesium diacrylate, aluminum diacrylate, aqueous solutions of metalacrylate monomers, among others. Zinc diacrylates and zincdimethacrylates (e.g., ZDA and ZDMA) are especially useful for curingepoxy functional systems.

ZDA and ZDMA containing compounds will cure the epoxy functionalcomponent of the formulas while being substantially free of conventionalcuring agents. By substantially free of conventional curing agents, itis meant that an epoxy functional compound (or other compound curablewith metal diacrylates or dimethacrylates), is cured while in thepresence of less than about 0.1 to about 1.0 wt. % (e.g., about 0% ofconventional epoxy curing agents) of the following compounds polyamides,dicyandiamides, imidizoles, imidizole compounds, amines, ureas, borontriflouride and complexes, polysulfides, anhydrides, melamines,amidoamines, phenol/formaldehyde, among other conventional curingagents. While the instant invention can be practiced in combination withsuch conventional curing agents, the instant invention obviates thenecessity of such compounds, among other benefits.

The epoxy functional systems of the instant invention may be used in awide range of applications such as automotive sealants, coatingsincluding corrosion resistant coatings, adhesives, pipeline treatment orwrap, powder paints/coatings/films, films, liquid sealers in combinationwith UV activated compounds to provide dual cure functionality such asdescribed in U.S. Pat. No. 6,461,691; hereby incorporated by reference(e.g., a system that is at least partially cured with UV and then heatedfor additional curing). These formulas are particularly useful inautomotive, electronic, industrial, aerospace, among other applications.

DETAILED DESCRIPTION

The instant invention relates to using metal diacrylate compounds suchas zinc diacrylate (ZDA), zinc dimethacrylate (ZDMA), mixtures thereof,among others for curing epoxy functional and other cross-linking orreactive compounds, and to systems containing such compounds (e.g.,epoxy powder coatings, films, sealers, etc.). The metal diacrylates canbe employed to cure a wide range of systems. Examples of such systemscomprise at least one curable polymer selected from the group consistingof polybutadiene, melamine, isocyanates, epoxy and epoxy functionalcompounds such as bis A, bis F, cycloaliphatic epoxy, novolac, epoxyesters, polyesters, acrylates, phenolic modified alkyds, alkyds, acrylicalkyd copolymers, among other systems. The amount of curable polymerwill normally range from about 1 to about 99 wt % (e.g., about 75 toabout 90 wt. %)

The use of metal diacrylates such as zinc diacrylate (ZDA), zincdimethacrylate (ZDMA), magnesium diacrylate, aluminum diacrylate,aqueous solutions of metal acrylate monomers, among others, as a curingagent, for example, epoxy functional systems (e.g., epoxy powdercoatings, films, etc.), can be an effective replacement fordicyandiamide, amine, polyamide, polysulfides, anhydrides, melamines,ureas, imidizole compounds, boron tri-fluoride and complexes,amidoamines, phenol/formaldehyde or other conventional heat activatedcures. The ability to reduce, if not eliminate, the usage ofconventional curing agents can reduce environmental hazards that havebeen associated with many conventional curing agents. The metaldiacrylate or dimethacrylate curing agents of the invention can beeasily blended with solid or liquid epoxy resins, or mixtures of liquidand solid resins in order to produce epoxy functional systems such asrelatively clear coatings, coatings with reduced shrinkage, differentcure responses, among other properties. The replacement of dicyandiamideor other conventional curing compounds with metal diacrylate ordimethacrylate can usually be accomplished without significant changesin the manner in which the epoxy functional systems are prepared. Theinventive epoxy functional systems are normally heat activated (e.g., ata temperature of about 300 F. to about 400 F. depending upon the lengthof heating time). However, the cure response of the metal diacrylate ordimethacrylate can also offer advantages over systems cured withdicyandiamide or other conventional cures. That is, the inventiveacrylates curing ability is a generally linear function of time vs temp,rather than a relatively sharp peak at the melt point of a curing agent(e.g., as with dicyandiamide agents). Clarity, adhesion and stability,compatibility with fillers such as high ph silicates, plastic, andmetallic powder, reactive resins among others, are aspects of the epoxyfunctional systems which can be improved with the inventive metaldiacrylate curing agent. Epoxy functional systems which incorporatemetal diacrylate or dimethacrylate as the curing mechanism havemechanical properties similar to conventionally cured formulas. The cureresponse is not dependent on melting point, but is normally time andtemperature dependent. This can be very advantageous for many processessuch as metal part painting, electronic component, aerospace, amongother uses. End use applications can achieve desired mechanicalproperties such as toughness and flexibility among others, by adjustingtime and temperature for each specific need.

The metal diacrylate can have a structure comprising:C₃H₄O_(2.1)/2M

wherein M can comprise at least one member selected from the groupconsisting of zinc (e.g., 2-propenoic acid zinc salt), aluminum,magnesium, tin, copper, nickel, aqueous solutions of acrylate (e.g.,aqueous solutions of metal acrylate monomer such as zinc acrylatemonomer), among others. While any suitable metal diacrylate or ZDA/ZDMAcompounds or modified ZDA/ZMA compounds can be employed, examples ofcommercially available ZDA/ZDMA products comprise: SR 633, SR634,CN9016, CN 2401, CN2400, PC 300, PRO 5903, M Cure 204, SR 705, SR 706,SR 709 and aqueous solutions of zinc acrylate and a non-metallicacrylate monomer such as CD-664 and CD665 all of which are availablefrom Sartomer, Exton Pa. 19341. Non-metallic acrylates (and othercompatible organic compounds) can be combined with the metal diacrylatein order to modify the system, increase cure rate or hardness, amongother beneficial improvements. The particle size of the metal diacrylateor dimethacrylate can be varied thereby permitting production of thinand thick film formulations (e.g., Sartomer® CN2400 and CN 2401 arecommercially available as liquids; SR 9016 comprises particles rangingfrom about 40 to about 50 microns and SR 633 comprises particles havinga standard 200 mesh). If desired, the metal diacrylate or dimethacrylatecan be dispersed or dissolved within at least one carrier prior tocompounding into a system, e.g., water and other solvents. When themetal diacrylate comprises ZDA/ZDMA, the amount of ZDA/ZDMA ranges fromabout 1 to about 75 wt. % and typically about 5 to about 20 wt. % ofmetal diacrylate (e.g., about 5 to about 10 wt. % for an epoxyfunctional system).

Without wishing to be bound by any theory or explanation it is believedthat suitable metal diacrylate compounds may induce co-polymerization ofan epoxide with the acrylic group through the nucleophilic MichaelAddition reaction. The epoxide curing may begin with an initiation stepof a proton addition to the oxirane ring. The proton can be taken fromany available donor, e.g. water (moisture), acid, amine or phenolicmodifier of the metal diacrylate. This first step can produce a reactiveintermediate, e.g. HOCH₂—CH—, that will further react with the protondonor group, another epoxide or any other nucleophilic reagent, such asacrylic double bonds of ZDA. Acrylic double bonds are the knownnucleophiles, e.g. acrylic acid will react with water under basicconditions, CH₂═CH—COOH+H₂O→HOCH₂—CH₂COOH.

Without wishing to be bound by any theory or explanation, it is alsobelieved that the reaction between the activated epoxide and thediacrylate could be as follows:HOCHRCH₂—+CH₂═CH—R→HOCH₂—CH₂—CH₂—CH(R)—→, etc.The aforementioned reaction between an epoxy functional compound and ametal diacrylate such as ZDA can produce a uniform clear solid formationhaving an improved thermal stability, e.g., due to the structure of anionomer with —Zn— in the main polymer chain.

In one aspect of the invention, the inventive curing agent reducesshrinkage in comparison to conventional curing agents. That is, epoxyfunctional resin compositions were observed to have less shrinkage whencompared to the same resin cured with dicyandiamide. Normally, systemscured with the inventive curing agent shrink less than 2% (e.g., incomparison to greater than about 2% to about 8% with conventional curingagents).

In one aspect of the invention, ZDA/ZDMA cured epoxy systems are morecompatible with additives and fillers. This allows greater versatilityin the formulation of epoxy, melamine, isocyanurates, polysiloxane,alkyds, phenolic modified alkyds, acrylic alkyd copolymers, polyesters,epoxy esters and polybutadiene containing systems, e.g., adhesives,sealers, coatings, among other systems. In contrast to conventionalcuring agents such as dicyandiamides, ZDA/ZDMA are more compatible withacid type, and high pH, among other fillers. For example, the inventivesystem permits curing epoxy containing systems that include high pHsilicate fillers (e.g., a system comprising epoxy, calcium silicate andmetallic diacrylate). Such systems are normally difficult, if notimpossible, to cure with conventional curing agents due to an undesiredreaction between dicyandimiade and calcium silicate (e.g., which causecompound to foam).

Formulations or systems of the instant invention can be compatible witha wide range of filler materials. Examples of such filler materialscomprise at least one from the group consisting of silicates such ascalcium, sodium, potassium, lithium, aluminum, magnesium, among others;trihydrates such as aluminum trihydrate; carbonates, bitumins (e.g.,gilsonite), clays, nitrides such as aluminum nitride, boron nitride andsilicon nitride, carbides such as silicon carbide, silica, metallicpowders (e.g., ferrous and non-ferrous metals such as copper, zinc,aluminum, iron, among others), among other fillers. In some cases, thefiller materials can be employed for modifying the torque tension (e.g.,for threaded fasteners), lubricity, wear resistance, colorants,conductivity, among other surface characteristics. The amount of fillercan vary depending upon the desired properties in the cured formulation,and will typically range from about 1 to at least 70 wt % (e.g,. about 5to about 25 wt. %).

Many current sealing tapes and structural adhesive tapes are formulatedusing epoxidized elastomers or epoxy elastomer blends. In many cases,additions of filler, thixotropes and pigments are added to achieve therequired texture, color, or other physical characteristics that arenecessary for application. The addition of these ingredients maydecrease the performance of the tape in application, especially instructural tapes or pastes. A reactive resin may be used in the powdercomposition of the instant invention as the filler or pigment componentin order to overcome the decrease in performance seen in conventionalcure systems. Examples of reactive resins comprise at least one memberselected from the group consisting of epoxy, phenoxy, acrylic urethane,mixtures thereof, among others. The amount of reactive resin normallycomprises about 10 to about 95 wt. % of the composition or system (e.g.,about 20 to about 50 wt. %). Curing of the composition containing thereactive resin may be accomplished by convection heating, inductionheating, radiant heating, radiation, among other methods.

The elevated temperature melt point of powder resins allows theincorporation of the powder resins in tape or paste formulas without theresin being dissolved into the composition. The resin remains suspendedin the tape or paste composition, and provides properties very similarto formulas using non-reactive fillers to adjust the consistency of thecomposition. When the tape or paste composition is heated to theactivation point of the reactive resin, increased strength and toughnessamong other properties can be greatly improved over formulas whichcontain non-reactive fillers. For example, a reactive resin systemcomprising ZDA is also thermosetting at a given application or heatingtemperature (e.g., a composition comprising epoxy resin and ZDA can beemployed as a filler in another formation).

Formulations or systems of the instant invention can be employed forobtaining a relatively clear or colorless product. In contrast toconventional curing agents that impart an amber or dark hue, theinventive formulations can be substantially clear (depending upon thethickness, formulation composition, among other parameters). Color ofepoxy formulations was measured in accordance with conventionalpractices and using the Gardner scale. Gardner color for dicyandiamidecured epoxy was 8-10 whereas Gardner color for same system but curedwith ZDA (e.g., commercially available from Sartomer as Sr9016), wasabout 2 to 4.

The instant invention can be employed for tailoring the curing rate.Conventional curing agents typically have a rapid cure which isundesirable for certain applications. The curing rate of the instantinvention can be increased by exposure to higher temperatures, anddecreased by lower temperatures. The ability to control curing rate (andtemperature) is desirable in that such permits finished coating surfacesto be optimized for smoothness, hardness, gloss, and clarity. Generallya higher curing temperature also results in an increased hardness.

The instant invention can be employed for tailoring the activationtemperature of formulations. The activation or curing temperature canrange from about 275 to about 425° F. depending upon the thickness,amount of curing agent, composition of system being cured, method ofheating, among other conventional variables. Generally a thinner coatingwill require less heat and time to cure, and the higher the curingtemperature the harder the resultant coating. Additions of titanates,zirconates, among other complexing agents can be used for lowering thecure temperature of the inventive formulations. The amount of complexingagent will normally range from about 1 to about 20 wt. % of thecomposition or formulation. For example, adding 1-5% of a commerciallyavailable titanate (Lica 38J supplied by Kenrich) is effective atlowering the cure temperature of formulations containing epoxyfunctional compounds as the base polymer (e.g., to a cure temperature toless than 250° F.).

In one aspect of the invention one or more additives are included in theinventive formulations. Examples of such additives comprise at least onemember selected from the group of fillers, metal powders (e.g., zinc,aluminum, iron, steel, copper, among other metal powders), magneticmaterials, ceramic powders, plastic powders, resins (e.g., silicone,silanes, polysiloxanes, titanates and zirconates), among others.Formulations incorporating at least one polysiloxane, at least onemetallic powder and at least one ceramic powder can be used whenincreased temperature resistance is desired (e.g., a coating orformulation formed into a tape and applied onto a pipeline). Theseadditives will normally comprise about 1 to about 25 wt. % of thecomposition.

In another aspect of the invention, the inventive system is placed(e.g., extruded, dipped, sprayed, brushed applied or wiped on), upon areinforcement. The reinforcement can be located upon or within theinventive blend, e.g., a sandwich or laminate structure. Thereinforcement permits easier handling during application and/ormanufacture, reduces flow (or sagging) when the inventive system isexposed to increased temperatures, increases tensile strength, improvesabrasion resistance, among other characteristics. Depending upon thedesired properties, e.g., temperature resistance, the reinforcementmaterial can comprise any suitable material. The reinforcement materialnormally comprises a scrim, web, matte, mesh, perforated orun-perforated polymer films, an unwoven or a woven assemblage, amongother fibrous or film type reinforcements. When employing a scrim as thereinforcement (e.g., a fiberglass scrim having generally round fibersand approximately 12 squares per inch), the reinforcement can have anopen surface area of greater than 20 to at least about 80%. When thereinforcement material comprises a perforated polymer or metallic film,the reinforcement material can have an open surface area or porosity ofabout 1 to at least about 80%. The open surface area also allows areinforced system to retain its flexibility. Examples of suitablereinforcement materials comprise fiberglass, polypropylene,polyethylene, polyester, fluoropolymers, graphite, plastics, Kevlar®,aluminum, steel, copper, brass, cheesecloth, mixtures thereof, amongother materials. Additional examples of reinforcement materials aredescribed in U.S. Pat. No. 6,034,002, issued Mar. 07, 2000 and entitled“Sealing Tape For Pipe Joints”, and U.S. Pat. Nos. 5,120,381 and4,983,449; each of the previous US Patents are hereby incorporated byreference. While the reinforcement material can have any suitableporosity or weave density, in most cases the porosity of thereinforcement material is such that the inventive composition isself-adhering (or self-sealing). For example when employing a reinforcedinventive composition as a pipe wrap, the composition at least partiallypasses through the material in a manner sufficient for the blend toadhere to itself as the blend is being wrapped around the pipe, e.g.,the blend passes through the reinforcement thereby permitting the blendto bond to itself. The self-adhering characteristic normally obviatesthe need for primers or pre-treatments, and increases the efficiencywith which the reinforced composition covers a surface. In anotherexample, bubbling or blistering of the tape or coating during the cureprocess can be reduced, if not eliminated, by employing a reinforcement.Reducing bubbling or blistering is particularly desirable if theinventive system is employed as a paintable automotive sealant (e.g.so-called automotive “roof ditch” sealant).

If desired, the reinforcement material can be coated or pretreated withan emulsion, dispersion, UV reactive (including reactive to sunlight),electron beam active, water or solvent based systems, 100% solids,powder coat systems, or other composition for sizing the reinforcementmaterial, e.g., the reinforcement material is coated with an emulsionfor increasing the rigidity of the material thereby permitting thematerial to be cut to a predetermined size or configuration. The coatingcan be applied by any suitable methods known in the art such as dipping,laminating, spraying, roller coating, among others. Examples of suitablecoatings for the reinforcement material comprise at least one ofpolyvinyl alcohol, ethylene vinyl acetate, acrylic, urethane, epoxy,polyurethane or latex emulsions. Another example of a suitable coatingfor the reinforcement material comprises oligomers, monomers, additives,and a photo-initiator (e.g., ionium salts).

In another aspect of the invention, formulations containing the metaldiacrylate curing agent have an improved shelf life relative toconventional curing agents. For example, the inventive formulation isstable for at least 120 days without special packaging or refrigerationwhereas formulations containing conventional curing agents are typicallystable for about 90 days.

In a further aspect of the invention, the inventive formulations orsystem are employed as a corrosion resistant coating. For example, azinc plated article or component treated in accordance with the processdescribed in U.S. Pat. Nos. 6,149,794; 6,258,243; 6,153,080; 6,322,687and PCT Patent Application Publications PCT/U.S.02/24716;PCT/U.S.02/24617 and PCT/U.S.02/24446 (all of which are herebyincorporated by reference), is coated with the inventive system. Thecoated article has increased corrosion resistance when measured inaccordance with ASTM B-117.

The inventive formulation can be employed for improving conventionalepoxy functional coatings. The inventive formulation can be used forcuring epoxy functional coatings such as e-coats, powder coatings,adhesives, among others. For example, an inventive coating comprising anepoxy powder and a metal diacrylate curing agent (e.g., ZDA andsubstantially free of dicyandiamides), can be applied or sprayed upon ametal article. The metal article is then heated in order to fuse andcure the epoxy coating. In one aspect, a ZDA containing epoxy powdercoating is applied onto a pipe, heat cured and then buried. By employingthe inventive coating, a tightly bonded coating can be obtained withoutusing curing agents such as dicyandiamides.

In another aspect of the invention, the inventive formulations orsystems can be modified by an additive comprising cubes or particulates.Particularly desirable results can be achieved by employing cubescomprising nylon 6/12, nylon 6/6 or other commercially availablematerials (e.g., 0.04/0.08/0.10 inch cubes available commercially fromMaxi-Blast). In some cases the cubes or media can comprise metallicmaterials such as copper, aluminum, among other metals (e.g., about 10to about 60 wt % metallic materials especially if improved conductivityis desired). The cubes function as an in situ dampener or spacer thatincreases the compressive strength of the inventive system. When thesystem is employed as a sealant (e.g., automotive sealant), the cubesreduce the tendency of the sealant to be forced out of a seam or jointformed between at least two members being sealed, e.g., two metalmembers. That is, the cubes define the minimum distance between twomembers such that the sealant is retained in the joint. Normally, theamount of this additive ranges from about 0.1 to about 5 wt. % of thesystem.

The combinations of the instant invention can be prepared by anysuitable method such as kneading, batch mixing, extrusion, among othermethods. While the above description has emphasized using the inventivecomposition for automotive and industrial coatings/paints/sealers,structural reinforcement, sealants and tapes, the instant invention canbe employed in wide array of application such as decorative crafts,glazing, concrete aggregate, gels, structural reinforcement, among otherapplications.

The combinations of the instant invention can be applied by any methodthat is conventional for a given end use such as manual or roboticapplications. If desired, the inventive combinations can be fabricatedinto a tape that is dispensed or applied by using the apparatus andmethod described in U.S. patent application Ser. No. 10/087,930(Sharpe); hereby incorporated by reference.

The following Examples are provided to illustrate certain aspects of theinstant invention and shall not limit the scope of any claims appendedhereto.

EXAMPLES

Examples 1-8 demonstrate ZDA/ZDMA compositions used for coatings. Thesecompositions were prepared by hand mixing or mechanical stirring (i.e.,an air motor with an impeller) in a beaker under ambient conditions.

Material Description Supplier wt percent Example 1 Uvacure 1500Cycloaliphatic Radcure 90% SR 633 Zinc Diacrylate Sartomer 10% Example 2Epalloy 8240 Novolac CVC specialties 90% SR 633 Zinc Diacrylate Sartomer10% Example 3 Epon 828 Bis A Resolution 90% SR 633 Zinc DiacrylateSartomer 10% Example 4 Epon 872 Bis F Resolution 90% SR 633 ZincDiacrylate Sartomer 10% Example 5 Ricon 100 Polybutadiene Sartomer 90%SR 633 Zinc Diacrylate Sartomer 10% Example 6 Aerotex 3030 MelamineCytec 90% SR 633 Zinc Diacrylate Sartomer 10% Example 7 Epon 828 Bis AResolution 90% PRO 5903 Mg Diacrylate Sartomer 10% Example 8 Epon 828Bis A Resolution 88% PC 300 Zinc Diacrylate Sartomer 10% Lica 38JTitanate Kenrich  2%

Examples 9-10 demonstrate ZDA/ZDMA containing systems that were preparedusing commercially available materials (e.g., Sartomer® ZDA's: SR 634,SR 9016, and CN 2400). Example 9 illustrates using the inventivecompositions to form a coating and Example 10 illustrates making a tapefrom the inventive compositions.

Example 9

The formula listed below was prepared and applied by hand onto a steelpanel and cured at 400° F. in air for 10 minutes.

Material Description Supplier wt. % Uvacure 1500 cycloaliphatic epoxyRadcure 44% Epon 8240 novolac epoxy CVC specialties 44% SR 9016 ZincDiacrylate Sartomer 10% Z 6040 silane Dow  2%

If desired, the above formula and other coatings disclosed herein can beemployed as a sealer or top coating for metallic surfaces previouslytreated in accordance with U.S. Pat. Nos. 6,149,794; 6,258,243;6,153,080; 6,322,687 and PCT Patent Application PublicationsPCT/US02/24716; PCT/US02/24617 and PCT/US02/24446; hereby incorporatedby reference.

Example 10

The inventive compositions can be fabricated into a tape. Such tapes canbe used for improving the corrosion resistance of a steel pipeline. Anexample of such usage is described in U.S. patent ApplicationPublication No. US-2002-0013389-A1; hereby incorporated by reference.These tape formulations, which are listed below in Tables 1 and 2, wereprepared by mixing in a Baker Perkins double arm mixer.

TABLE 1 Material Description Supplier wt. % Vamac G ethylene acrylicrubber DuPont  7.5% ZOCO 104 zinc oxide ZOCO 1.25% Gilsonite MPgilsonite Lexco 12.5% Hubersorb 600 calcium silicate Huber 12.5% SU 2.5epoxy Resolution   25% Trilene 65 EPDM rubber Uniroyal 37.5% SR633 zincdiacrylate Sartomer 3.75%

TABLE 2 Material Description Supplier wt. % Vamac G ethylene acrylicrubber DuPont   10% ZOCO 104 zinc oxide ZOCO    1% Z 6018 polysiloxaneDow corning 12.25% HM 443 metallic powder Hoosier   47% LERE HHepoxy/phenoxy Inchemrez   20% Viton A fluoro elastomer Dupont DowElastomers    5% SR633 zinc diacrylate Sartomer  3.75% Lica 38J titanateKenrich    1%

Examples 11-13

Examples 11-13 demonstrate using ZDA containing materials as areinforcement material, e.g., a material applied onto an automotivecomponent wherein the material becomes rigid after exposure to heatingin a paint oven (e.g., refer to U.S. Pat. Nos. 5,040,803; 5,151,327,5,755,486; all of which are hereby incorporated by reference). Thesematerials comprised modified and unmodified epoxy resins as a base ormaster batch to which mineral fillers and nitrile rubber were added fordimensional control during forming, handling, vehicle installation,among other purposes. Three materials having the formulations listed inTable 3 below were prepared by mixing in a sigma blade mixer withsubsequent heated pressing to obtain a composite comprising a laminatewith fiberglass cloth reinforcement. The composite was applied to coldrolled steel test panels and baked at 350° F. for 30 minutes. Theflexural strength of the baked test panels was measured on an Instrontensile testing machine in accordance with conventional procedures withthe resulting in the data listed below in Table 4.

TABLE 3 Formulations Example 11 Example 12 Example 13 MaterialDescription Supplier (%) (%) (%) NySyn 33-3 Nitrile Rubber ZeonChemicals 6.96 6.81 6.66 Epon 58005 CTBN Rubber Modified Bis-AResolution 9.05 8.85 8.66 Epoxy SB 222 Alumina Trihydrate J. M. Huber10.72 10.49 10.26 Isolene 400 Polyisobutylene (Liquid) Elementis 5.575.45 5.33 Specialties Epon 872 Bis-A Epoxy Resolution 11.14 10.9 10.66InChemRez LER-HH Phenoxy modified Bis-A Epoxy Phenoxy Associates 20.0519.61 19.19 Epon 834 Bis-A Epoxy Resolution 15.59 15.25 14.93 3M K37Glass Hollow Glass Spheres 3M 22.28 21.79 21.33 Bubbles Cab-O-Sil TS720Silane Treated Fumed Silica Cabot 1.78 1.74 1.71 Black Carbon BlackCabot 0.89 0.87 0.85 Sartomer SR633 Zinc Diacrylate Sartomer 2.23 4.366.40

TABLE 4 Flexural Strength (Pounds) Example 11 Example 12 Example 1330.61 36.52 36.78Table 4 illustrates an increase in flexural strength. Without wishing tobe bound by any theory or explanation, it is believed that the increasein flexural strength is caused by curing or cross-linking the epoxyresins during the bake process. While there are no adverse affects,Table 4 indicates that no additional flexural strength is achieved byadding greater than about 20 parts (6.5%). In addition to improving theflexural strength, ZDA additions increased adhesion with the cold rolledsteel substrate, i.e., all three formulations demonstrated cohesivebonds to the cold rolled steel substrate.

Examples 14-20

Examples 14-20 demonstrate applying the inventive compositions onto azinc substrate that had been pretreated in a silicate-containing medium(i.e., known as the EMC™ process). The coatings were either mixed byhand or mixed with a high-speed disperser. The pretreatment process isdescribed in U.S. Pat. Nos. 6,149,794; 6,258,243; 6,153,080; 6,322,687and PCT Patent Application Publications PCT/U.S.02/24716;PCT/U.S.02/24617 and PCT/U.S.02/24446; hereby incorporated by reference.The inventive coatings were applied onto 2″×3″ zinc plated substrates.The substrates were cleaned with isopropyl alcohol prior to coating. Thesubstrate was dipped into the coating for approximately 10 sec. Thecoated substrate was removed and hung vertically. The coating was curedfor 20 min. at 340° F. The coating compositions used in Examples 14-20and evaluation of the coating effectiveness are listed below (CRS=ColdRolled Steel).

Material Example 14 Example 15 Example 16 Epon 828  50 g  50 g  20 g(Epoxy from Resolution) Erisys EMRM-20  15 g (Elastomer Modified Epoxyfrom CVC Specialty) Cardura E-10P  25 g  35 g  55 g (Glycidyl Ester fromResolution) Veova 10  25 g  25 g (Vinyl Ester from Resolution) DAPROU-99 0.2 g (Interfacial Tension Modifier from Elementis) Z6040 0.2 g 0.2g (Silane from Dow Corning) SR 706  20 g  15 g  10 g (Modified MetallicDiacrylate from Sartomer) Cured Properties Surface Cure Good Good GoodCross Hatch Adhesion: Good: 0% Coating Good: 0% Coating Good: 0% CoatingInitial (CRS) Loss Loss Loss Cross Hatch Adhesion: Good: 0% Coating — —Initial (EMC) Loss

Material Example 17 Example 18 Epon 828  50 g  50 g (Epoxy fromResolution) Veova 10  50 g  50 g (Vinyl Ester from Resolution) DAPROU-99   1 g (Interfacial Tension Modifier from Elementis) Z6040 0.2 g 0.2g (Silane from Dow Corning) SR 706  10 g  10 g (Modified MetallicDiacrylate from Sartomer) Surface Cure Good Good Cross Hatch Adhesion:Initial (CRS) Good: 0% Coating Loss Good: 0% Coating Loss Cross HatchAdhesion: Initial — Good: 0% Coating Loss (EMC)

Material Example 19 Example 20 Epon 828 50 g 50 g (Epoxy fromResolution) Veova 10 50 g 50 g (Vinyl Ester from Resolution) BaghouseFines  3 g (Sodium Silicate) Supernat D10  3 g (Synthetic AmorphousSilicon Dioxide from Degussa) DAPRO U-99  1 g  1 g (Interfacial TensionModifier from Elementis) Z6040  1 g  1 g (Silane from Dow Corning) SR706 10 g 10 g (Modified Metallic Diacrylate from Sartomer) Pre-Bake NoneNone Surface Cure Good Good Cross Hatch Adhesion: Initial Good: 0%Coating Loss Good: 0% Coating Loss (CRS) Flexibility Good: 90° with nocracks but has Good: 90° with no cracks but has some signs of stress.Has good some signs of stress. Has good adhesion at the bend, also looksadhesion at the bend, also looks good at 180° good at 180°

Examples 21-25

Tables #1 and 2 demonstrate powder coat and film adhesive formulations.The powder coat formulations of Table 1 were prepared by heating theepoxy (or phenoxy) resin components to about 140C in order to melt thesolid epoxy and the epoxy components were mixed to form a homogenousmixture. The diacrylate was added and mixed into the molten epoxymixture (or phenoxy mixture), and then the mixture was force cooled on achilled plate. The cooled mixture was ground with a ball mill to form apowder having a mesh of about 200 mesh.

The film of Table 2 as prepared by combining and heating and cooling themixtures as previously described in connection with the powder coatformulations of Table 1. The powder was then placed between releasepapers and converted into a film on a heated Carver Lab Press. A film ofabout 10 mils in thickness was produced. Thinner films can be obtainedby applying greater pressure.

TABLE #1 Example Powder Coat Formulas Compound Compound Description Wt %Supplier Example 21 Epon 1002 Solid epoxy resin 90 Resolution SR 9016Metal diacrylate 10 Sartomer Example 22 Epon 1007 Solid epoxy 60Resolution Epon 828 Liquid epoxy 30 Resolution SR 9016 Metal diacrylate10 Sartomer Example 23 Epon 1009 Solid epoxy 50 Resolution Epon 828Liquid epoxy 40 Resolution SR 9016 Metal diacrylate 10 Sartomer Example22 was repeated with the exception that the solid epoxy was replacedwith phenoxy resin.

TABLE #2 Example Adhesive Film Formulations Compound CompoundDescription Wt % Supplier Example 24 Epon 1009 Solid epoxy 40 ResolutionEpon 828 Liquid epoxy 40 Resolution TC 140 Ethylene methyl 10ExxonMobile acrylate SR 9016 Metal diacrylate 10 Sartomer Example 25Epon 1007 Solid epoxy 20 Resolution Epon 1002 Solid epoxy 20 ResolutionEpon 828 Liquid epoxy 40 Resolution TC 140 Ethylene methyl 10ExxonMobile acrylate SR 9016 Metal diacrylate 10 Sartomer

Examples 26-32

This Example demonstrates using metal acrylates for curing systems otherthan epoxy functional systems, and that the cure temperature can affectcuring. The formulations listed below were mixed 10 in a plastic cup byhand. Approximately 7-10 g of the blend was poured into a tin lid(≈50.15 mm diameter x≈7.5 mm height). The material was then cured at adesignated temperature and time. Observations were made for signs ofcuring. Observations were also made for shrinkage.

Formulation Example 26 Example 27 Example 28 Example 29 Chempol 211-336910 g (High Solids Polyester from Cook Composites & Polymers) Chempol812-2218 10 g (High Solids Phenolic Modified Alkyd from Cook Composites& Polymers) Chempol 910-0453 10 g (Water Reducible Epoxy Ester from CookComposites & Polymers) Chempol 810-0089 10 g (Water Reducible ChainStopped Alkyd from Cook Composites & Polymers) SR 705  1 g  1 g  1 g  1g (Metallic Diacrylate from Sartomer) Cure Observations 275 F./15 mins275 F./15 mins 275 F./15 mins 275 F./15 mins No Signs of Cure No Signsof Cure Partial Cure Partial Cure Cure Observations 350 F./15 mins 350F./15 mins 350 F./15 mins 350 F./15 mins Very Slight Cure Very SlightCure Good Cure Good Cure No Shrinkage Noticed No Shrinkage Noticed

Formulation Example 30 Example 31 Example 32 Chempol 810-1537 10 g(Acrylic Alkyd Copolymer from Cook Composites & Polymers) Chempol816-1200 10 g (High Solids Epoxy Ester Adduct from Cook Composites &Polymers) Chempol 210-9889 10 g (Water Reducible Polyester from CookComposites & Polymers) SR 705  1 g  1 g  1 g (Metallic Diacrylate fromSartomer) Cure Observations 350 F./ 350 F./ 350 F./ 15 mins 15 mins 15mins Partial to Partial to Very Slight Good Cure Good Cure Cure No NoShrinkage Shrinkage Noticed Noticed

While the apparatus, compositions and methods of this invention havebeen described in terms of preferred or illustrative embodiments, itwill be apparent to those of skill in the art that variations may beapplied to the process described herein without departing from theconcept and scope of the invention. All such similar substitutes andmodifications apparent to those skilled in the art are deemed to bewithin the scope and concept of the invention and the appended claims.

1. A film adhesive comprising a heat curable composition comprising atleast one epoxy functional compound, and about 5 to about 20 wt. percentof at least one metal acrylate curing agent and wherein the compositionis substantially free of conventional curing agents.
 2. The filmadhesive of claim 1 comprising a heat curable composition comprising atleast one curable compound, and at least one curing agent selected fromthe group consisting of metal acrylates, metallic diacrylates, metallicdimethacrylates and metallic monomethacrylate wherein the composition issubstantially free of peroxides, amines, polyamides, dicyandiamide,polysulfides, anhydrides, melamines, ureas, anhydrides, imidazole andimidazole compounds, boron trifluoride and complexes, amidoamines, andphenol/formaldehydes.
 3. The film adhesive of claim 1 wherein the filmadhesive is reinforced.
 4. The film adhesive of claim 3 wherein thereinforcement comprises at least one member selected from the groupconsisting of scrim, web, matte, mesh, perforated or unperforated filmsand woven or unwoven assemblage.
 5. The film adhesive of claim 1 whereinthe epoxy functional compound comprises at least one member selectedfrom the group consisting of polybutadiene, melamine, isocyanates, bis Aepoxy, bis F epoxy, cycloaliphatic epoxy, novolac compounds, epoxyesters, alkyds and alkyd functional materials, polyesters and acrylates.6. The film adhesive of claim 1 wherein the film adhesive furthercomprises at least one filler selected from the group consisting of atleast one silicate, silica, trihydrates, carbonates, bitumins, andclays.
 7. The film adhesive of claim 1 wherein the composition furthercomprises at least one filler material selected from the group ofreactive resin composition.
 8. The film adhesive of claim 1 wherein thefilm adhesive further comprises at least one additive selected from thegroup consisting of metal powders, magnetic materials, ceramic powders,plastic powders and resins.
 9. The film adhesive of claim 1 wherein thecomposition further comprises at least one reinforcement.
 10. The filmadhesive of claim 9 wherein the reinforcement comprises at least one offibers or film.
 11. The film adhesive of claim 2 further comprising atleast one complexing agent selected from the group consisting ofzirconates and titanates.
 12. The film adhesive of claim 1 wherein themetal acrylate curing agent comprises at least one member selected fromthe group consisting of zinc diacrylate, zinc dimethacrylate, magnesiumdiacrylate, mixtures thereof and aqueous solutions thereof.
 13. The filmadhesive of claim 2 wherein the metal acrylate curing agent comprises atleast one of zinc diacrylate and dimethacrylate.
 14. The film adhesiveof claim 12 wherein the metal acrylate curing agent comprises at leastone of zinc diacrylate, zinc dimethacrylate and magnesium diacrylate.15. The film adhesive of claim 1 further comprising at least one memberselected from the group consisting of silanes and polysiloxanes.
 16. Apowder coat comprising a heat curable composition comprising at leastone epoxy functional compound, and about 5 to about 20 wt. percent of atleast one metal acrylate curing agent and from about 20 to about 50 wt.percent of a reactive resin and wherein the composition is substantiallyfree of conventional curing agents.
 17. The powder coat of claim 16wherein the coating comprises at least one member selected from thegroup consisting of epoxy functional e-coatings and epoxy functionalpowder coatings.
 18. The powder coat of claim 16 wherein the reactiveresin is selected from the group consisting of epoxy, phenoxy, acrylicurethane and mixtures thereof.
 19. The powder coat of claim 16comprising a heat curable composition comprising at least one curablecompound, and at least one curing agent selected from the groupconsisting of metal acrylates, metallic diacrylates, metallicdimethacrylates and metallic monomethacrylate wherein the composition issubstantially free of peroxides, amines, polyamides, dicyandiamide,polysulfides, anhydrides, melamines, ureas, anhydrides, imidazole andimidazole compounds, boron trifluoride and complexes, amidoamines, andphenol/formaldehydes.